Surface biactive amphoteric agents



United States Patent 3,336,372 SURFACE BIACTIVE AMPHOTERIC AGENTS PhilipG. Abend, Cleveland Heights, Ohio, and Warner M. Linfield, Evanston, andBelen C. Brown, Chicago, Ill., assignors to Armour and Company, Chicago,Ill., a corporation of Delaware No Drawing. Filed Dec. 23, 1963, Ser.No. 332,938 Claims. (Cl. 260-501) This invention relates to surfacebiactive amphoteric agents, and, more particularly, to amphotericsurface active agents which possess both detergent and fabric softeningproperties.

While the desirability of providing a single surfactant which wouldprovide both detergent and fabric softening properties has beenrecognized, yet it was thought that the specific diverse attributes ofsuch a surfactant necessary to produce respective detergency andsoftening were normally not compatible in a single compound. Detergencyhas been usually, though not exclusively, attributed to the so-calledanionic surfactants, while fabric softening has been generallyattributed to the cationic surfactants. Yet it has been furthergenerally accepted that anionic surfactants are not normally compatiblewith cationic materials and are frequently precipitated from solutionsby cationic materials and even by certain inorganic cations such asaluminum, calcium, magnesium, etc., with which they combine to formcompounds having little or no surface activity.

Therefore, one object of this invention is to provide a class ofcompounds in which each compound is amphoteric in the sense that itpossesses both the anionic attribute of detergency and the cationicproperty of fabric softening, and in which the respective anionic andcationic centers are compatible and do not become ineffective as aresult of precipitation in solution.

Also, it is a further object of this invention to provide surfacebiactive amphoteric agents which minimize the undesirablecharacteristics of yellowing, waterproofing, and soil redeposition onmultiple application, and which may be used as the active component of aheavy-duty liquid detergent softener formulation.

The surface biactive amphoteric agents which we have obtained have incommon the following structural formula:

In the foregoing formula, R is an alkyl group containing from 12 to 18carbon atoms, R is a hydrocarbon chain which is either an alkylenecontaining from 2 to 6 carbon atoms or a phenyl alkylenecontaining from2 to 4 carbon atoms in the alkylene chain, and R is an alkyl groupcontaining from 1 to 8 carbon atoms, or, a hydroxy alkyl groupcontaining from 2 to 8 carbon atoms in the chain with the hydroxyl groupin the number two position from the nitrogen atom. It is'to beunderstood in the foregoing, that while R is an alkyl group containingfrom 12 to 18 carbon atoms, such as stearyl or palmityl, for bestsoftening properties stearyl is to be preferred.

The surface biactive amphoteric agents having this chain structuralformula possess both detergency and softening properties. As isobservable from the formula, compounds 0 ia av C H S O aNa Patented Aug.15, 1967 possessing both softening and detergency properties appear todemonstrate a ratio of the number of fatty chains to cationic centers of1:1.

In obtaining the surface biactive amphoteric agents with which thisapplication is concerned, we first synthesized compounds as follows:

EXAMPLE 1 Synthesis of the bis-Schic base(p,p'-xylylidinea,a'-bis-octadecylam ine) A mixture of terephthalicaldehyde (0.25 m., 35.5 g), octadecylamine (0.50 m., 134 g.) and 200mls. of benzene was refluxed with azeotropic removal of water. Afterone-half hour of refluxing, 10 mls. of water had distilled over. 100mls. of benzene were drawn off and refluxing was continued for 15minutes more. The mixture was cooled, diluted with 800 mls. of acetoneand kept in the freezer for 18 hours. The precipitate was filtered,washed with acetone and dried. Yield: 152 g. This synthesis may beexpressed by the following:

EXAMPLE 2 Synthesis of the bis-amino sulfonate (p,p'-xylylene-a,o'-bis-octadecylamina-disodiumw -sulfonate) A mixture of the bis-Schiifbase (P. 0835 m., 53 g.), prepared as described in Example 1, an aqueoussolution of sodium bisulfite (0.167 m., 33.4 mls. of a 5 M solution) and150 ml. of ethanol was refluxed for one hour. The mixture was cooled,diluted with 400 mls. of acetone, kept in the freezer for a few hours,filtered and dried. Yield: 70.5 g. This synthesis may be expressed bythe following:

Synthesis of the amphoteric(p,p'-xylylene-'a,a'-bisdim'ethyloctadecylamm0nium-a,a-sulf0nate) Amixture of the bis-amino sulfonate (0.0818 m., 69 g.), prepared asdescribed in Example 2, 500 mls. of isopropanol and 2 mls. ofphenolphthalein indicator was heated to 70 C. Dimethyl sulfate (0.328m., 42 g.) and a 30% aqueous solution of sodium hydroxide (0.164 m.,6.55 g.) was added dropwise simultaneously to the bisamino sulfonate sothat the mixture was just slightly pink. All the sodium hydroxidesolution was added when about one-half of the dimethyl sulfate was in.Addition of the dimethyl sulfate was continued, the total addition timebeing one hour. The mixture was then refluxed for one-half hour C.) andfiltered while hot.

The filtrate (a yellow solution) was evaporated to dryness, then takenup in 200 mls. of ethyl acetate, heated to boiling and filtered. Thefiltrate was kept in the freezer for 16 hours. The product, a whitesolid, was filtered, washed well with acetone and dried. Yield: 57 g.This synthesis may be expressed by the following:

CH1: SOa

- 3 EXAMPLE 4 Synthesis of 2-butyne-L4-bis (dimethyloctadecylammoniumchloride) A mixture of 1,4-dichlorobutyne-2 (12.3 g., 0.10 m.),dimethyloct-adecylamine (59.4 g., 0.20 m.), 400 ml. of n-propyl alcoholand 25 ml. of water was refluxed for 8 hours. The solvent was removed byevaporation under reduced pressure and the residue extracted with 200ml. of hot ethyl acetate. The solution was cooled to C. for 16 hours andthe resulting crystals filtered, washed with petroleum ether, thenair-dried. Yield: 50 g. of a 100% active product. This synthesis may beexpressed by the following:

After these compounds were prepared, they were then tried on soiledfabrics under actual washing conditions and the evaluation of therepresentative detergency and softening properties made. Therepresentative compounds which resulted from the syntheses set forth inExamples 3 and 4 demonstrated both detergency and softening properties.

Additional examples of bis-amphoteric compounds can be prepared asfollows:

EXAMPLE 5 Synthesis of butane-1,4-bis(diethyldodecylammonium)2,3-disulfonate Reflux a mixture of 1,4-dichlorobutylne-2 (12.3 g., 0.10mole), diethyldodecylamine (48.2 g., 0.20 mole), 400 ml. n-propanol and25 ml. of water for 8 hours. Remove the solvent by evaporation underreduced pressure and extract the residue with 200-250 ml. of hot ethylacetate. Cool the solution to 0 C. until crystallization of theintermediate bis-quaternary salt occurs. This material may be filtered,washed with petroleum ether, and used as is for the second step of thepreparation. Reflux a mixture of crude2-butyne-1,4-bis(diethyldodecylammonium chloride) (30.2 g., 0.05 mole),200 ml. of n-propanol, sodium bisulfite (20.8 g., 0.20 mole), and 400ml. of water for 5 hours. Remove the solvent by evaporation underreduced pressure and extract the residue with 300 ml. of isopropanol.The product may be precipitated by pouring the isopropanol solution into1 liter of acetone. This bisamphoteric is filtered and air-dried.

EXAMPLE 6 Synthesis of butane-1,4-bis(bis (Z-hydroxyethyl)dodecylammonium 2,3-disulfonate Reflux a mixture of 1,4-dichlorobutyne-2(12.3 g., 0.10 mole), bis(2-hydroxyethy1) dodecylamine (57 g., 0.20mole), 400 ml. n-propanol and 25 ml. of water for 8 hours. Isolate theintermediate bis-quaternary and treat with four equivalents of sodiumbisulfite as in preparation of Example 5.

EXAMPLE 7 Synthesis of butane-1,4-bis(di-n-hexyld0decylammonium)-2,4-disulfonate Reflux a mixture of 1,4-dichloro-butyne (12.3 g., 0.10mole), di-n-hexyldodecylamine (71 g., 0.20 mole), 400- 500 ml. ofn-propanol, and 25 ml. of water. Isolate the intermediate bis-quaternaryand react it with four equivalents of sodium bisulfite as in thepreparation of Examples 5 and 6.

While in the foregoing specification this invention has been describedin relation to certain preferred embodiments and many details have beenset forth for purpose of illustration, it will be apparent to thoseskilled in the art that the invention is susceptible to additionalembodiments and that certain of the details set forth herein can bevaried considerably without departing from the basic principles of theinvention.

We claim:

1. As new compositions of matter, the class of compounds represented bythe structural formula wherein R is an alkyl group containing from 12 to18 carbon atoms and R is a hydrocarbon chain selected from the classconsisting of alkylene containing from 2 to 6 carbon atoms and phenylalkylene containing from 2 to 4 carbon atoms in the alkylene chain and Ris selected from a :grOup consisting of an alkyl containing 1 to 8carbon atoms and a hydroxy alkyl having 2 to 8 carbon atoms with thehydroxyl in the number two position from the nitrogen atom.

2. The class of compounds of claim 1 wherein R is alkylene containingfrom 2 to 6 carbon atoms.

3. The class of compounds of claim 1 wherein R is phenyl alkylenecontaining from 2 to 4 carbon atoms in the alkylene chain.

4. As a new composition of matter, the compound represented by thestructural formula:

5. As a new composition of matter, the compound represented by thestructural formula:

6. As new compositions of matter, the class of compounds represented bythe structural formula:

CH3 so. CH;

1t s1- r-N C 131 37 CH: 303 CH;

wherein R is alkylene containing from 2 to 6 carbon atoms.

7. As new compositions of matter, the class of compounds represented bythe structural formula:

References Cited FOREIGN PATENTS 10/1957 Germany.

OTHER REFERENCES Schwartz et al.: Surface Active Agent and Detergents,vol II 1953 page 140.

Moilliet et al.: Surface Activity (1961), page 399.

LORRAINE A. WEINBERGER, Primary Examiner.

MARY B. WEBSTER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,336,372 August 15 1967 Philip G. Abend et al It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 1, lines 65 to 67, the formula should appear as shown belowinstead .of as in the patent:

C H NHCH CHNH-C H 4 (CH SO ZNaOH fi SO Na O Na bis column 2 line 9 for"bis-Schic", in italics read the formula,

Schiff in italics column 4 lines 43 to 46 in for "S0 each occurrenceread SO Signed and sealed this 25th day of June 1968.

(SEAL) Attest:

EDWARD J. BRENNER EDWARD M.FLETCHER,JR.

Commissioner of Patents Attesting Officer

1. AS NEW COMPOSITIONS OF MATTER, THE CLASS OF COMPOUNDS REPRESENTED BYTHE STRUCTURAL FORMULA